Cleaning implement comprising a modified open-cell foam

ABSTRACT

The present invention relates to a cleaning implement that includes a melamine-formaldehyde foam. The melamine-formaldehyde foam includes from about 0.1 to about 5 weight % of at least one linear polymer with a number average molecular weight M n  in the range from 500 to 10,000 g/mol. Additionally the present invention encompasses processes for making and methods for cleaning hard surfaces with a cleaning implement according to the present invention.

TECHNICAL FIELD

The present invention relates to cleaning implement based onmelamine-formaldehyde foams. The melamine-formaldehyde foam includesfrom about 0.1 to about 5 weight % at least one linear polymer.

BACKGROUND OF THE INVENTION

Recently, a novel application for such melamine-formaldehyde foams inthe area of hard surface cleaning has been discovered. Indeed, cleaningimplements of cut or molded pieces of such melamine-formaldehyde foam,and in particular melamine foam, have become popular to remove soilsand/or stains from hard surfaces (i.e., cleaning of hard surfaces) suchas tiles, walls, floors, sanitary fittings such as sinks, showers,shower curtains, wash basins, WCs, household appliances including, butnot limited to, refrigerators, freezers, washing machines, automaticdryers, ovens, microwave ovens, dishwashers and so on. Indeed, melaminefoam sponges are currently marketed under the tradename Mr. Clean MagicEraser®.

It is has been observed that melamine-formaldehyde foam in particularshows good soil and/or stain removal performance when used to clean hardsurfaces, on stains/soils such as marks on walls and furniture. Indeed,it has been observed that melamine foam in particular, when wetted withan appropriate solvent, such as tap water, removes soils and/or stainsfrom a hard surface when said hard surface is brought into contact withsaid wetted modified open-cell foam. By “bringing into contact” it ismeant wiping, swiping, rubbing or the like. In order for the melaminefoam in particular to optimally remove soils and/or stains from hardsurfaces substantial amounts of an appropriate solvent, such as tapwater, have to be used. Most commonly, tap water is used by the users ofmelamine foam when removing soils and/or stains from hard surfaces. Whenused with water or any other appropriate solvent, the melamine foam inparticular comes off as small particles (meaning, the foam crumbles)when brought into contact with a hard surface. Indeed, a milkysuspension of small modified melamine foam in particular particles inwater is formed. However there has been the need for better soil and/orstain removal with better durability upon use.

It is therefore, an objective of the present invention to provide acleaning implement, wherein said implement is capable of (improved)cleaning greasy soap scum soils and neat kitchen dirt (grease) from hardsurfaces whilst providing a good surface safety profile and at the sametime showing excellent durability upon use.

It has been now found that above objective can be met by use of cleaningimplement that includes a melamine-formaldehyde foam that comprises atleast one linear polymer. Indeed, the objectives are met by cleaningimplements according to present invention based on suchmelamine-formaldehyde foam, the method of cleaning hard surfaces withsuch a cleaning implement or the method of cleaning hard surfaces withthe melamine-formaldehyde foams according to present invention.

The articles, processes and uses according to the present invention willnow be described.

SUMMARY OF THE INVENTION

The present invention relates to a cleaning implement that includes amelamine-formaldehyde foam. The melamine-formaldehyde foam includes fromabout 0.1 to about 5 weight % of at least one linear polymer with anumber average molecular weight M_(n) in the range from 500 to 10,000g/mol.

The present invention further encompasses processes for making andmethods for cleaning hard surfaces with a cleaning implement accordingto the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of a cleaning implement 1.

FIG. 2 is a perspective view of a cleaning implement 1 comprising twolayers.

FIG. 3 is a graphical representation of compression deflection forceversus d90/d10 ratio of the cleaning implement of the claimed inventionand various commercially available implements.

DETAILED DESCRIPTION OF THE INVENTION

Cleaning Implement

The cleaning implement 1 herein is based on the melamine-formaldehydefoam comprising at least one liner polymer.

By a “cleaning implement” it is meant herein an article of manufactureof any suitable shape and/or size and/or volume suitable for cleaning,i.e., removing spots and/or stains from hard surfaces. In a highlypreferred embodiment according to the present invention, the cleaningimplement herein is in a shape and/or size and/or volume suitable foruse by a consumer to clean hard surfaces therewith. Examples of cleaningimplements are wipers, brushes, cleaning cloths or cleaning granules.

In a preferred embodiment, the cleaning implements herein are suitablefor cleaning/cleansing inanimate surfaces selected from the groupconsisting of household hard surfaces; dish surfaces; surfaces likeleather or synthetic leather; and automotive vehicles surfaces.

In a highly preferred embodiment, the cleaning implements herein aresuitable to clean household hard surfaces.

By “household hard surface”, it is meant herein any kind of surfacetypically found in and around houses like kitchens, bathrooms, e.g.,floors, walls, tiles, windows, cupboards, sinks, showers, showerplastified curtains, wash basins, WCs, fixtures and fittings and thelike made of different materials like ceramic, vinyl, no-wax vinyl,linoleum, melamine, glass, Inox®, Formica®, any plastics, plastifiedwood, metal or any painted or varnished or sealed surface and the like.Household hard surfaces also include household appliances including, butnot limited to refrigerators, freezers, washing machines, automaticdryers, ovens, microwave ovens, dishwashers and so on. Such hardsurfaces may be found both in private households as well as incommercial, institutional and industrial environments.

Suitable shapes of the cleaning implements 1, such as a wiper, hereinmay be selected from the group consisting of: cube shape, rectangularshape, pyramid shape, cylindrical shape, cone shape, pencil erasershape, cuboid shape, tetrahedron shape; sphere shape; globular shape;and ellipsoid shape. Preferably, said cleaning implement has a shapeselected from the group consisting of: cube shape, rectangular shape,pencil eraser shape, and cuboid shape.

Suitable volumes of the cleaning implements herein may be from 1 cm³ to10,000 cm³, preferably from 10 cm³ to 1,000 cm³, more preferably from 90cm³ to 250 cm³.

In a highly preferred embodiment herein, the cleaning implement 1 hereinhas a cuboid shape defined by three groups of parallel and equal lengthsides, referred to as a, b and c, wherein a ranges from 2 cm to 20 cm,preferably 4 cm to 8 cm, b ranges from 2 cm to 20 cm preferably 8 cm to15 cm, and c ranges from 1.5 cm to 5 cm, preferably 2 cm to 4 cm.

The cleaning implement 1 of a first embodiment of the present inventionas shown in FIG. 1 comprises a single layer 2 of melamine-formaldehydefoam comprising at least one linear polymer.

In a preferred embodiment according to the present invention thecleaning implements herein may comprise additional layers of material.Preferably, in the cleaning implement herein said melamine-formaldehydefoam 2 comprising at least one linear polymer forms a first layer andsaid cleaning implement additionally comprises a second layer ofmaterial. Even more preferably, said second layer of material is asecond foam layer 3 made of a second foam material as discussed hereinbelow. Such a cleaning implement according to this preferred embodimentis shown in FIG. 2.

The layers of melamine-formaldehyde foam 2 comprising at least onelinear polymer and second foam 3 may be arranged in said cleaningimplement in any way suitable. In a preferred embodiment according topresent invention the layers of melamine-formaldehyde foam 2 comprisingat least one linear polymer and second foam 3 are arranged parallel toat least one side, preferably two opposite sides, of the cleaningimplement. However, the cleaning implement may also have an irregularshape. Indeed, the thickness of the layers may be constant or varythroughout the cleaning implement. The separation line 4 between the twolayers may form a straight line or may form a bend or be completelyirregular. In addition, the separation plane of the layers may be in thecenter of cleaning implement, dividing the implement in two equal parts,or may be in the upper or lower part of the implement. In addition, thecleaning implement may be in the shape of a sphere or a globule or anellipsoid with the separation plane of the layers forming a sphericalsegment or one of the layers, preferably the layer of a second foamhere, forming a sphere in a sphere (similar to the layers of an onion).

In this highly preferred embodiment of the present invention, whereinthe cleaning implement 1 herein has a cuboid shape, the line indicatingthe separation 4 of the two layers (or the surface areas where the twolayers are joined together) of the implement is preferably substantiallyparallel (preferably parallel) to the side of the cuboid shapedimplement having the largest surface area (as shown in FIG. 2).

In another highly preferred embodiment herein the cleaning implementherein is in the shape of a pencil eraser. By “shape of a pencil eraser”it is meant herein a voluminous body having six walls, wherein threepairs of parallel and equally shaped and sized walls exist and whereinone pair of walls are in the shape of a parallelogram and the remainingtwo pairs of walls are of rectangular shape. In this preferredembodiment, wherein the cleaning implement herein has the shape of apencil eraser, the line indicating the separation of the two layers (orthe surface areas where the two layers are joined together) of theimplement is preferably substantially parallel (preferably parallel) tothe side of implement in the shape of a pencil eraser having the largestsurface area.

In order to obtain suitable cleaning implements according to a preferredembodiment of the present invention, the melamine-formaldehyde foamlayer 2 comprising at least one linear polymer and the second layer ofsecond foam 3 have to be attached to each other. This attachment can beachieved by any attachment means suitable for joining the two layers.The attachment may be either a permanent attachment (wherein the twolayers cannot be separated without inflicting substantial damage to thelayers) or temporary attachment (wherein the two layers may be separatedwithout inflicting substantial damage to the layers). Suitableattachment means providing a permanent attachment are selected from thegroup consisting of: foam flame laminating the two layers together; useof a permanent adhesive; sewing the two layers together; andneedle-punching the two layers together; and combinations thereof.Suitable attachment means providing a temporary attachment are selectedfrom the group consisting of: a weak adhesive; Velcro; and awater-based, water-soluble coating or adhesive; and combinationsthereof.

In a preferred embodiment here, the attachment of layers herein is apermanent attachment.

Foam flame lamination is a continuous process that can adhere foams andadditional materials, if any, to one or both sides of foam in a singlepass. The process of flame lamination involves the passing of first foam(either the melamine-formaldehyde foam comprising linear polymer hereinor the second foam herein) over an open flame, which creates a thinlayer of molten foam/polymer. Second foam (either the second foam hereinor the melamine-formaldehyde foam comprising linear polymer herein,depending on the first step) is pressed against the first foam while itis still in the molten state. Foams and additional material, if any, canbe adhered to one or both sides of the foam in a single pass.Furthermore, additional passes are optional. The strength of the bonddepends upon the foams and additional material, if any, selected and theprocessing conditions (i.e., gas type, flame height and spread, foamburn-off and nip pressure).

The cleaning implement according to the present invention may containmore than two layers, wherein said additional layers, if, any, may be ofthe same or similar materials as the melamine-formaldehyde foamcomprising at least one linear polymer or said second foam, or may bemade of another material having similar properties as said second foamor different properties therefore. Indeed, the cleaning implement hereinmay be in a so-called sandwich configuration, wherein three layers arepresent. In a preferred embodiment, wherein the cleaning implementherein is in a sandwich configuration, the middle layer may be saidsecond foam and at least one of the two outer layers ismelamine-formaldehyde foam comprising at least one linear polymer withthe second outer layer being either melamine-formaldehyde foamcomprising at least one linear polymer or another material providingother feature, such as abrasiveness or increased rigidity. In a highlypreferred embodiment according to the present invention the cleaningimplement herein comprises two outer layers of saidmelamine-formaldehyde foam comprising at least one linear polymer and aninner layer, preferably of a second foam material, as discussed hereinbelow.

The layers of the cleaning implement according to the present inventionmay cover each other either partially or fully. By a “partial coverage”it is meant that at least one of the layers overlaps the other layer (orother layers, if any) and is not fully covered by said other layer (orother layers, if any). By a “full coverage” it is meant that the layersof the cleaning implement do fully cover each other and that none of thelayers substantially overlap the other layer (or other layers, if any).

The ratio of said melamine-formaldehyde foam comprising at least onelinear polymer to said second foam in the cleaning implement accordingto the present invention is preferably from 20:1 to 1:20 by volume, morepreferable from 10:1 to 1:10 by volume, even more preferably 5:1 to 1:1,still more preferably 5:1 to 2:1, and most preferably from 4:1 to 3:1 byvolume.

In order to obtain suitable cleaning implements according to the presentinvention, the melamine-formaldehyde foam comprising at least one linearpolymer—and second foam-raw materials may have to be modified in shapeand/or size. This modification can be done by any means known to thoseskilled in the art. Suitable means of modifying the shape and/or size ofmelamine foam- and second foam-raw materials may be selected from thegroup consisting of: cutting, breaking, and tearing, and combinationsthereof.

Melamine-formaldehyde foams as such and their production and also linearpolymers as such and their production are known to a person skilled inthe art and described in the literature.

The melamine-formaldehyde foams of the present invention comprise atleast one linear polymer. The at least one linear polymer preferably hasan average number molecular weight M_(n) in the range from 1000 to 8000g/mol. Most preferably the linear polymer has a number average molecularweight M_(n) in the range from 3000 to 5000 g/mol. The number averagemolecular weight M_(n) can be calculated from the OH number according toDIN 53240. Preferably 0.1 to 5 parts by weight, more preferably 0.3 to 2parts of the at least one linear polymer is used per 100 parts ofmelamine-formaldehyde precondensate. Preferably, the linear polymer ishydrophilic. The water solubility of the linear polymer preferably ismore than 5% per weight, more preferably more than 10% per weight.Preferably, the linear polymer comprises at least a terminal hydroxylgroup. The linear polymer consists preferably of the elements carbon,hydrogen and oxygen. Most preferably, polyethylene glycol is used as thelinear polymer.

The melamine-formaldehyde foams of the present invention comprising atleast one linear polymer are preferably obtainable by the consecutiveprocess steps a) and b):

-   -   a) heating to foam up and crosslink a mixture comprising a        melamine-formaldehyde precondensate having a molar ratio of        melamine:formaldehyde in the range of typically from 1:1.3 to        1:5 and preferably from 1:2.5 to 1:3.5, at least one linear        polymer, a curative, a dispersant and a blowing agent, and    -   b) drying the foam obtained in process step a),        wherein these process steps and also the melamine-formaldehyde        precondensates, curatives, dispersants and blowing agents useful        in step a) are known in principle to a person skilled in the art        and are described in the literature.

The melamine-formaldehyde precondensate in addition to melamine andformaldehyde may comprise up to 50% by weight and preferably up to 20%by weight (all based on the weight of cocondensed melamine) of otherthermoset-formers and up to 50% by weight and preferably up to 20% byweight (all based on the weight of cocondensed formaldehyde) of otheraldehydes in cocondensed form. Useful thermoset-formers include forexample: alkyl- and aryl-alkyl-substituted melamine, urea, urethanes,carboxamides, dicyandiamide, guanidine, sulfurylamide, sulfonamides,aliphatic amines, glycols, phenol and its derivatives. Examples ofuseful other aldehydes are acetaldehyde, trimethylolacetaldehyde,acrolein, benzaldehyde, furfurol, glyoxal, gluteraldehyde,phthalaldehyde and terephthalaldehyde. Particular preference is given toan unmodified melamine-formaldehyde precondensate, i.e., amelamine-formaldehyde precondensate devoid of any otherthermoset-formers or other aldehydes. Further details concerningmelamine-formaldehyde condensation products may be found in Houben-Weyl,Methoden der organischen Chemie, volume 14/2, 1963, pages 319 to 402.

Commercially available melamine-formaldehyde precondensates are usefulfor a multiplicity of fields of use, for example for further processinginto glues. Melamine-formaldehyde precondensates comprising sulfitegroups are advantageous for use in some of these fields. Such sulfitegroup-containing melamine-formaldehyde precondensates are obtainable forexample as described in EP-B 37470 whereby from 1% to 20% by weight ofsodium disulfite is incorporated in the course of the condensation ofmelamine and formaldehyde to obtain cocondensed sulfite groups.

For the processes of the present invention, however, it is advantageousthat step a) utilizes a precondensate which is free of the sulfitegroups.

Emulsification of the blowing agent and stabilization of the foam instep a) requires the addition of a dispersant, e.g., an emulsifier oremulsifier mixture. Useful emulsifiers include anionic, cationic andnonionic surfactants and also mixtures thereof.

Suitable anionic surfactants are diphenylene oxide sulfonates, alkane-and alkylbenzenesulfonates, alkylnaphthalenesulfonates,olefinsulfonates, alkyl ether sulfonates, fatty alcohol sulfates, ethersulfates, alpha-sulfo fatty acid esters, acylaminoalkanesulfonates, acylisethionates, alkyl ether carboxylates, N-acylsarcosinates, alkyl andalkyl ether phosphates. Useful nonionic surfactants include alkylphenolpolyglycol ethers, fatty alcohol polyglycol ethers, fatty acidpolyglycol ethers, fatty acid alkanolamides, EO-PO block copolymers,amine oxides, glycerol fatty acid esters, sorbitan esters andalkylpolyglucosides. Useful cationic emulsifiers includealkyltriammonium salts, alkylbenzyldimethylammonium salts andalkylpyridinium salts. The emulsifiers are preferably added in amountsof 0.2% to 5% by weight, based on the melamine-formaldehydeprecondensate.

For the melamine-formaldehyde precondensate, which is preferably used inthe form of an aqueous solution or dispersion, to produce foam in stepa), it has to comprise a blowing agent, the amount depending on thedesired density of the foam. In principle, the process of the presentinvention can utilize both physical blowing agents and chemical blowingagents. Useful physical blowing agents include, for example,hydrocarbons, halogenated and more particularly fluorinatedhydrocarbons, alcohols, ethers, ketones and esters in liquid form or airand CO₂ as gases. Useful chemical blowing agents include, for example,isocyanates mixed with water, in which case CO₂ is released as aneffective blowing agent, moreover carbonates and bicarbonates mixed withacids, which likewise produce CO₂, and also azo compounds, such asazodicarbonamide. In one preferred embodiment of the present invention,the aqueous solution or dispersion of the melamine-formaldehydeprecondensate is admixed with between 1% and 40% by weight, based on themelamine-formaldehyde precondensate, of a physical blowing agent havinga boiling point of between 0 and 80° C.; in the case of pentane, theamount used is preferably in the range from 5% to 15% by weight.

Curatives used in step a) comprise acidic compounds catalyzing thecontinued condensation of the melamine-formaldehyde precondensate. Theamounts are between 0.01% and 20% by weight and preferably between 0.05%and 5% by weight, based on the melamine-formaldehyde precondensate.Organic and inorganic acids can be used, examples being hydrochloricacid, sulfuric acid, phosphoric acid, nitric acid, formic acid, aceticacid, oxalic acid, toluenesulfonic acids, amidosulfonic acids and alsoacid anhydrides.

The aqueous solution or dispersion of the melamine-formaldehydeprecondensate used in step a) is preferably free of further addedsubstances. However, it can be beneficial for some purposes to add up to20% by weight, and preferably less than 10% by weight, based on themelamine-formaldehyde precondensate, of customary added substances, suchas dyes, flame retardants, UV stabilizers, agents to lower combustiongas toxicity or to promote carbonization. Since the foams are generallyopen celled and capable of imbibing water, some applications make itnecessary to add hydrophobicizers in amounts of 0.2% to 5% by weight.Useful hydrophobicizers include for example silicones, paraffins,silicone surfactants, fluorosurfactants, hydrophobic hydrocarbonaceoussurfactants, silicone emulsions and fluorocarbon emulsions.

The concentration of the melamine-formaldehyde precondensate in themixture of precondensate and solvent/dispersant, more particularlywater, can vary within wide limits between 55% and 85% by weight andpreferably between 63% and 80% by weight, all based on the total weightof melamine-formaldehyde precondensate and solvent/dispersant. Thepreferred viscosity of the mixture of precondensate andsolvent/dispersant is between 1 and 3000 dPa·s and preferably between 5and 2000 dPa·s.

Further mixture components may be mixed with the aqueous solution ordispersion of the melamine-formaldehyde precondensate to form ahomogeneous mixture, with the blowing agent being forced in underpressure if necessary. However, it is also possible to start with asolid, for example spray-dried, melamine-formaldehyde precondensate andto subsequently mix it with a dispersion of the linear polymer and/orwith an aqueous solution of the emulsifier, with the curative and alsowith the blowing agent. After mixing, the heated resin mixture with thedispersed blowing agent is discharged through a die and foams upthereafter.

Foaming of the blowing agent-containing solution or dispersion uponemergence from the die is augmented—as described in EP-B 17671—by meansof hot air or high frequency irradiation. Preferably, the energy can beinput by electromagnetic radiation, for example by high frequencyirradiation with 5 to 400 kW, preferably 5 to 200 kW, particularlypreferably 9 to 120 kW per one kilogram of the mixture used in afrequency range of 0.2 to 100 GHz, preferably 0.5 to 10 GHz. Magnetronsare a suitable source of radiation for dielectric radiation, with one ormore magnetrons being able to be irradiated at the same time.

The mixture to be foamed is irradiated immediately on emerging from thefoaming die. The blowing agent evaporates the resin mixture foams up andat the same time cures through.

The foams produced are finally dried to remove water and blowing agentremaining in the foam.

In a further embodiment of the process according to the presentinvention, process step b) may be followed by a process step c) in whichthe dried foam is press molded to make it elastic.

Process step c) is known in principle to a person skilled in the art andis described in the literature, for example in EP-A 1 505 105 and EP-B37470.

The foam blocks or sheets obtained can optionally be thermocompressed ina further process step. Thermocompression as such is known to a personskilled in the art and described for example in WO 2007/031944, EP-A 451535, EP-A 111 860 and U.S. Pat. No. 6,608,118.

In a preferred embodiment, the process comprises the steps of:

-   -   a) producing an aqueous mixture M comprising        -   100 parts by weight of at least one melamine-formaldehyde            precondensate,        -   2 to 4 parts by weight, preferably 2.2 to 3.8 parts by            weight and more preferably 2.7 to 3.3 parts of at least one            curative,        -   0.2 to 5 parts by weight, preferably 0.5 to 3 parts by            weight and more preferably 1.25 to 2.3 parts by weight of a            surfactant mixture,        -   0.1 to 5 parts by weight, preferably 0.5 to 4 parts by            weight and more preferably 1.1 to 3.6 parts by weight of at            least one salt of an inorganic acid and/or of an organic            carboxylic acid,        -   1 to 40 parts by weight, preferably 10 to 35 parts by weight            and more preferably 15 to 21 parts of at least one blowing            agent,        -   0.1 to 5 parts by weight, preferably 0.3 to 2 parts off at            least one linear, polymer with an average molecular weight            (number average) M_(n) in the range from 500 to 10.000            g/mol, preferably in the range from 3000 to 5.000 g/mol.        -   25 to 60 parts by weight, preferably 30 to 50 parts by            weight and more preferably 36 to 44 parts of water,    -   b) heating and foaming said mixture M using microwave radiation,    -   c) annealing the foam using hot air and/or nitrogen in a        temperature range from 150° C. to 290° C.,

In general, the melamine-formaldehyde foams according to the presentinvention have a density of 3 to 100 kg/m³, preferably 5 to 50 kg/m³,more preferably 8 to 12 kg/m³.

As shown in FIG. 3's graphical representation of compression deflectionforce versus d90/d10 ratio, the melamine-formaldehyde foam of theclaimed invention (Sample 4) provide increased robustness as compared tovarious commercially available and other implements (Samples 1, 2, 3, 5and 6). Specifically, the melamine-formaldehyde foam of the presentinvention preferably have a d90/d10 ratio above 1.65, more probablyabove 1.7, and most preferably above 1.8 and preferably have acompression deflection force above 3.25 psi, more probably above 3.75psi and most preferably above 4.25 psi.

According to the present invention the melamine-formaldehyde foamscomprising linear polymer are obtainable batch wise or preferablycontinuously as sheets or webs generally in any desired thickness,advantageously in layered thicknesses ranging from 0.1 to 500 cm,preferably from 0.5 to 200 cm, more preferably from 1 to 100 cm, moreparticularly from 3 to 80 cm and most preferably from 5 to 50 cm.Moldings comprising melamine-formaldehyde foams according to the presentinvention are obtainable in a continuous manner or preferably in a batchwise manner.

The melamine-formaldehyde foams in the form of webs, sheets, moldings orsome other form can be laminated or endowed with surface layers bygenerally customary methods on one, two, more or all sides, for examplewith paper, paper board, glass overlay mat, wood, plaster board, metalsheet or metal foil, plastic or self-supporting plastics foam/sheetwhich may optionally also be foamed. The surface layers can be appliedin the course of foaming or subsequently. In the case of subsequentapplication, it is advantageous to use an adhesion promoter.

The cleaning implement based on melamine-formaldehyde foams comprisingat least one linear polymer are used for cleaning hard surfaces.

Second Layer

In a highly preferred embodiment, as discussed above, the cleaningimplement 1 herein may comprises (at least) one additional layer 3. Thesecond layer 3 may comprise a foam, a film, a synthetic nonwoven, acellulosic sheet, sustainable sheets and combinations thereof. Plurallayers may comprise one or more of these materials and laminatesthereof, including the same and/or different materials.

If a foam is selected for one or more of the layers, suitable foams areselected from the group consisting of polyurethane foams; polypropylenefoams; polyethylene foams; cellulose foam sponges; naturally occurringsponges; open-cell polyester foams; and cross-linked polyethylene foams;and combinations thereof.

If a film is selected for one or more of the layers, the layer maycomprise a polyolefinic sheet, as is known in the art. The sheet maycomprise polyethylene terephthalate, polypropylene, polyethylenenaphthalate, low-density polyethylene, high-density polyethylene, etc.as are known in the art. The film layer may be smooth or textured, asdescribed in commonly assigned U.S. Pat. No. 4,846,821. A film layer mayhave a basis weight of about 15 to about 60 gsm and/or a thicknessranging from about 0.01 to about 3 mm.

A synthetic nonwoven may be carded, thermally bonded, spunbonded,hydroentagled, etc., as are known in the art. The nonwoven may be ofconstant or variable basis weight and/or density. The nonwoven may betextured and/or comprise discrete apertures, as disclosed in commonlyassigned U.S. Pat. No. 6,936,330. A nonwoven layer may have a basisweight of about 15 to about 120 gsm and/or a thickness ranging fromabout 0.01 to 3 mm.

A cellulosic sheet may be wet laid and comprise permanent and/ortemporary wet strength resins, as are known in the art. The cellulosicsheet may comprise kraft grade or tissue grade paper. The cellulosicsheet may be of constant or variable basis weight and/or density, asdisclosed in commonly assigned U.S. Pat. No. 5,277,761 or commonlyassigned U.S. Pat. No. 4,637,859. A tissue grade cellulosic sheet mayhave a basis weight of about 15 to about 45 gsm and/or a thicknessranging from about 0.01 to about 3 mm.

If desired, the one or more of the layers may be made of sustainablematerials and/or combinations and blends of sustainable and othermaterials, including polymers derived from Biorenewable materials.Sustainable materials may include polylactic acid (PLA), polyglycolicacid (PGA), polybutylene succinate (PBS), an aliphatic-aromaticcopolyester optionally with high terephthalic acid content, an aromaticcopolyester optionally with high terephthalic acid content,polyhydroxyalkanoate (PHA), thermoplastic starch (TPS) and mixturesthereof. Suitable materials are disclosed in commonly assigned U.S. Pat.No. 8,083,064.

If desired, the layer may comprise a laminate of two or more materials.For example, the second layer 3 may comprise a layer of polyolefinicfilm. This layer may be reinforced with a woven layer or yarn layerattached thereto. A woven layer may comprise a loose weave, providingloop material suitable for attachment to a hook surface. A yarn layermay comprise plural parallel or randomly laid yards, also providing loopmaterial suitable for attachment to a hook surface. The woven and/oryarn layers may be thermally bonded to the second layer 3.

In another embodiment the second layer 3 may comprise any sheet which isflexible, impermeable to fluid and, in one embodiment, hydrophobic. Asused herein, the term “impermeable” means that the material resists and,in some embodiments, prevents diffusion of moisture therethrough.

The thickness of said second layer 3, if any, is preferably up to 30 mm,preferably from 0.5 mm to 20 mm, more preferably from 1 mm to 15 mm,even more preferably from 2 mm to 10 mm, and most preferably from 4 mmto 8 mm. Furthermore, in the preferred embodiment herein, wherein thecleaning implement comprises a second layer 3 the thickness of saidlayer is preferably from 7 mm to 100 mm, more preferably from 15 mm to25 mm.

In a preferred embodiment herein, the total volume of said second layer3 in the cleaning implement herein is preferably from 10 cm³ to 100 cm³,more preferably from 20 cm³ to 70 cm³, even more preferably from 30 cm³to 60 cm³, and most preferably from 40 cm³ to 50 cm³.

Benefit Agent

The cleaning implements herein may contain a benefit agent, locatedanywhere as known in the art. In one embodiment, the active agent isimpregnated in the melamine-formaldehyde foam layer 2 comprising thelinear polymer. In another embodiment, the benefit agent is embedded inthe second foam layer 3. In yet another embodiment, the benefit agent isimpregnated in the attachment means, as discussed above, that attachesthe foam layer 2 to the foam layer 3. It will be understood, however,that in still further embodiment that the benefit agent can be locatedin any or all of the foam layer 2, foam layer 3 or attachment means, asknown in the art. Suitable benefit agents are selected among asurfactant, a bleaching agent, a limescale reducing agent, a biocide, asolvent, a polymer, a solid, a colorant and mixtures thereof. In oneembodiment, the benefit agent may have an HLB greater than about 5,alternatively greater than about 8 to about 14, alternatively greaterthan about 12. In another embodiment, the benefit agent may be presentin free form in an amount from about 5% to about 20%, or from about 10%to about 15% by weight of the benefit agent. A benefit agent in freeform means that the benefit agent is supplied to the cleaning implementin its neat form whose release from the cleaning implement is notpurposefully controlled, delayed, or sustained. In some preferredembodiments, the benefit agent(s) is supplied to the cleaning implementin forms, as known in the art, such that the release from the cleaningimplement is purposefully controlled, delayed, or sustained.

Surfactants that are suitable for the present invention can be nonionic,anionic, cationic, amphoteric and/or a zwitterionic surfactant. Suitablenonionic surfactants include alkoxylated fatty alcohol having theformula of RO(EO)e(PO)pH, where R is a hydrocarbon chain of from 2 to 24carbon atoms, EO is ethylene oxide and PO is propylene oxide, e and prespectively representing the average degree of ethoxylation andpropoxylation, are independently from 0 to 24, or R is a straight alkylchain having from 6 to 22 carbon atoms, e is 5-12 and p is 0 (e.g.Lutensol™). Suitable cationic surfactants herein include derivatives ofquaternary ammonium, phosphonium, imidazolium and sulfonium compounds.Preferred cationic surfactants herein are trimethyl quaternary ammoniumcompounds. Suitable amphoteric surfactants herein include amine oxides,betaine or ammonium sulfate or ammonium carboxylate, having thefollowing formula R₁R₂R₃NO, R₁R₂R₃NR₄SO₄ or R₁R₂R₃NR₄CO₂ wherein each ofR₁, R₂ and R₃ is independently a saturated substituted or unsubstituted,linear or branched alkyl groups of from 1 to 30, or from 8 to 18 carbonatoms, except for R₄ which preferably contain 3 saturated carbons.Preferred amine oxides herein are for instance natural blend C₈-C₁₀amine oxides, and C₁₂-C₁₆ amine oxides, such as cetyl dimethyl amineoxide. Preferred betaine herein is cocamidopropyl betaine andlauramidopropyl betaine. Suitable anionic surfactants include alkyldiphenyl ether sulphonate and alkyl carboxylate. Other suitable anionicsurfactants herein include water soluble salts or acids of the formulaROSO₃M wherein R is preferably a C₁₀-C₂₄ hydrocarbyl, or C₁₂-C₁₈ alkylor hydroxyalkyl, and M is H or a cation, such as sodium, potassium,lithium, or ammonium or substituted ammonium. Other suitable anionicsurfactants include soap salts, C₉-C₂₀ linear alkylbenzenesulfonates,C₈-C₂₂ primary or secondary alkylsulfonates, sulfonated polycarboxylicacids, C₈-C₂₄ alkylpolyglycolethersulfates (containing up to 10 moles ofethylene oxide); alkyl ester sulfonates, sulfates ofalkylpolysaccharides, alkyl polyethoxy carboxylates, such as those ofthe formula RO(CH₂CH₂O)_(k)CH₂COO⁻M⁺ wherein R is a C₈-C₂₂ alkyl, k isan integer from 0 to 10, and M is a soluble salt-forming cation. Resinacids and hydrogenated resin acids are also suitable. Further examplesare given in “Surface Active Agents and Detergents” (Vol. I and II bySchwartz, Perry and Berch). A variety of such surfactants are alsogenerally disclosed in U.S. Pat. No. 3,929,678.

Bleaching agents herein may be selected from a hydrogen peroxide source,a preformed peroxycarboxylic acid, a hypohalite bleach source, and amixture thereof. Hydrogen peroxide sources herein include persulfate,dipersulphate, persulfuric acid, percarbonate, perborate, metalperoxide, perphosphate, persilicate, urea peroxyhydrate and a mixturethereof. Preformed peroxycarboxylic acids herein include thosecontaining one, two or more peroxy groups, and can be aliphatic oraromatic. When the organic percarboxylic acid is aliphatic, theunsubstituted acid suitably has the linear formula:HO—O—C(O)—(CH₂)_(n)—Y, wherein Y is H, CH₃, CH₂Cl, COOH or C(O)OOH; n isan integer of 1-20. Branched analogs are also acceptable. When theorganic percarboxylic acid is aromatic, the unsubstituted acid suitablyhas formula: HO—O—C(O)—C₆H₄—Y wherein Y is hydrogen, alkyl, alkyhalogen,halogen, —COOH or —C(O)OOH. Monoperoxycarboxylic acids useful as oxygenbleach herein are further illustrated by alkyl percarboxylic acids andaryl percarboxylic acids such as peroxybenzoic acid and ring-substitutedperoxybenzoic acids, e.g., peroxy-α-naphthoic acid; aliphatic,substituted aliphatic and arylalkyl monoperoxy acids such asperoxylauric acid, peroxystearic acid, andN,N-phthaloylaminoperoxycaproic acid (PAP); and6-octylamino-6-oxo-peroxyhexanoic acid. Peracids can be used in acidform or any suitable salt with a bleach-stable cation. Suitablehypohalite bleaching agents herein include those that form positivehalide ions and/or hypohalite ions, and bleaching agents that areorganic based sources of halides, such as chloroisocyanurates. Suitablehypohalite bleaching agents herein include alkali metal and alkalineearth metal hypochlorite, hypobromite, hypoiodite, chlorinated trisodiumphosphate dodecahydrate, potassium and sodium dichloroisocyanurates,potassium and sodium trichlorocyanurates, N-chloroimides,N-chloroamides, N-chloroamines and chlorohydantoins.

Limescale reducing agents herein include, but are not limited to, acidsand chelating agents. Exemplary acids useful herein include hydrochloricacid, phosphoric acid, sulfuric acid, sulfamic acid, acetic acid,hydroxyacetic acid, citric acid, benzoic acid, tartaric acid, formicacid and mixtures thereof. A mixture of organic and inorganic acid ispreferred. Chelating agents useful herein can include, but are notlimited to, carboxylates, phosphates, phosphonates,polyfunctionally-substituted aromatic compounds, polyamines,biodegradable compounds, the alkali metal, ammonium or substitutedammonium salts or complexes of these chelating agents, and mixturesthereof. Further examples of suitable chelating agents and levels of useare described in U.S. Pat. Nos. 3,812,044; 4,704,233; 5,292,446;5,445,747; 5,531,915; 5,545,352; 5,576,282; 5,641,739; 5,703,031;5,705,464; 5,710,115; 5,710,115; 5,712,242; 5,721,205; 5,728,671;5,747,440; 5,780,419; 5,879,409; 5,929,010; 5,929,018; 5,958,866;5,965,514; 5,972,038; 6,172,021; and 6,503,876.

Biocide means any known ingredient having the ability of reducing oreven eliminating by killing or removing the micro-organisms existing ona surface, such as those described in U.S. Pat. No. 6,613,728. Biocideuseful herein includes a quaternary surface active compound, aguanidine, an alcohol, a glycerol, a phenolic compound, a heavy metalsalt, an inorganic and organic acid, a halogen, a halogen-containingcompound, a dye, an essential oil, an oxidizing compound, an adsorbent,a fungicide, an algaecide and a mixture thereof. Exemplary quaternarysurface active compounds include benzalkonium chloride, benzethoniumchloride, cetyl pyridinium chloride, sodium tetradecyl sulfate,sichlorobenzalkonium chloride, methylbenzethonium chloride, cetyldimethyl ethyl ammonium bromide. Exemplary guanidines includechlorohexidine hydrochloride, chlorohexidine gluconate, dodecylguanidinehydrochloride, polyhexmethylenebiguanidine hydrochloride, and6-acetoxy-2,4-dimethylmetadioxane. Exemplary alcohols include methanol,ethanol, propanol, isopropanol, etc. Exemplary phenolic compoundsinclude cresol, resolcinols and related compounds, phenol; substitutedphenols—cresols, meta-cresylacetate, creosote, quaiacol, resorcinol,hexylresorcinol, pyrogallol, thymol, thymol iodide, picric acid,chlorinated phenols—dichlorophene, hexachlorophene, tars. Exemplaryhalogens and halogen-containing compounds include iodine and iodoform.Exemplary oxidizing agents include peroxide, sodium perporate, potassiumpermanganate, zinc permanganate, potassium chlorate. Exemplary heavymetal salts include mercuric chloride, miscellaneous ionizable mercuricsalts, organic mercurials, silver nitrate, silver lactate, silverpicrate, silver proteins, silver halides, zinc oxide, zinc stearate,copper sulfate and organic tin derivatives. Exemplary dyes include azodyes, acridene dyes, fluorescein dyes, phenolphthalein dyes andtriphenylmethane dyes. Exemplary inorganic and organic acids includehydrochloric acid, sulfuric acid, nitric acid, citric acid, sorbic acid,acetic acid, boric acid, formic acid, maleic acid, adipic acid, lacticacid, malic acid, malonic acid, glycolic acid, and mixtures thereof.Exemplary essential oils are thyme oil, clove oil, cinnamon oil,geranium oil, eucalyptus oil, peppermint oil, citronella oil, ajowanoil, mint oil or mixtures thereof. Other useful biocide herein includesfuran derivatives, nitrofurantoin, sulfur, sulfur dioxide, ichthamol,chrysarobin, anthralin, betanaphthol, balsams, volatile oils,chlorophyl.

Biocides useful herein also include fungicides and algaecides which actagainst molds and mildew. Removal of algae and fungi from hard surfacesis difficult. Moreover, fungi and algae reappear promptly if notcompletely removed or inhibited. Suitable fungicides and algaecidesinclude metal salts, such as zinc sulfate, zinc acetate, zinc bromide,zinc chloride, zinc iodide, zinc nitrate, zinc bromate and zincchlorate, cooper halide, copper sulfate, organic tin derivatives,water-insoluble or partially water-soluble fungicides and algaecides,such as diiodomethyl p-tolyl sulfone, N-(trichloromethyl thio)phthalimide, N,N-dimethyl-N-phenyl N′-(fluorodichloromethyl thio)sulphamide, 2-(thiocyanomethylthio)benzothiazole/methylenebis(thiocyanate), 3-iodo-2-propynyl butyl carbamate, etc., all availablefrom ALDRICH chemical. Above biocides are optionally mixed withconcentrated acids, such as acetic acid, formic, propionic, n-butanoic,n-pentanoic, trimethylacetic, n-hexanoic, lactic, methoxyacetic,cyanoacetic, chloroacetic, citric, partaric, etc.

The benefit agent may be a solvent having a good dissolving ability forgreasy stains. Solvents useful herein include those which are at leastpartially water-miscible, such as alcohols, ethers, such as diethyleneglycol diethylether, diethylene glycol dimethylether, propylene glycoldimethylether, propylene glycol monomethylether, propylene glycolmonoethylether, propylene glycol monopropylether, propylene glycolmonobutylether, ethylene glycol monobutylether, dipropylene glycolmonomethylether, dipropylene glycol monopropyl ether, dipropylene glycolmonobutyl ether, diethyleneglycol monobutylether, lower esters ofmonoalkylethers of ethylene glycol or propylene glycol, such aspropylene glycol monomethyl ether acetate, N-methyl pyrolidone andtetrahydrofuran. Mixtures of several solvents can also be used.

Polymers useful herein include polyolefins, polyesters, polyvinylchlorides, polyamides, mixtures thereof and copolymers thereof. Specificexamples of useful polymers include but are not limited topolypropylene, polyethylene, polybutylene, polystyrene, polyethyleneterephthalate, polyamide, polyacrylate, polyvinyl chloride, polyvinylalcohol, ethylene vinyl acetate copolymers and mixtures thereof.

Useful solids include abrasive materials or fillers which may beinorganic or organic materials, e.g. sand, lime (CaCO₃), silicates withan average particle diameter (number-average) in the range from about 1μm to about 1 mm, or colloidal silica, preferably inorganic material areselected from oxides, chlorides, sulfates, phosphates, carbonates of Mg,Mn, Ba, Ca, W, Zr, Ti, Si, Mo, in particular TiO₂, SiO₂, sand and Al₂O₃.Other suitable materials are insoluble sodium polymetaphosphate,hydrated alumina, dicalcium orthophosphate dihydrate, calciumpyrophosphate, tricalcium phosphate, calcium polymetaphosphate. Otherabrasive material may be Carbon based materials: i.e.: as referred asblack carbon, activated carbon, charcoal, etc. and may be porous or not.Other abrasive material include microspheres. Particularly preferredinorganic fillers are selected from zeolite based materials and silicabased materials. Suitable zeolite based materials are described in thefollowing reference texts: ZEOLITE SYNTHESIS, ACS Symposium Series 398,Eds. M. L. Occelli and H. E. Robson (1989) pages 2-7; ZEOLITE MOLECULARSIEVES, Structure, Chemistry and Use, by D. W. Breck, John Wiley b Sons(1974) pages 245-250, 313-314 and 348-352 (all of which are incorporatedherein by reference). SiO₂ exists in a variety of crystalline forms andamorphous modifications, any of which are suitable for use herein. Inparticular, silicas having a high surface area or in agglomerated formsare preferred (i.e., clays or shells). Without being restrictive to afamily of silica based materials, commonly silica which is in a highlypurified form such that is contains at least about 90%, preferably about95%, more preferably about 99% silicon dioxide (i.e.: a silica gelhaving a about 100% silica content, and fumed silica) is preferred.Alternatively, silica based materials may be provided from other sourcessuch as metal silicates including sodium silicate. Further suitablematerials are water-insoluble sodium polymetaphosphate, hydratedalumina, dicalcium orthophosphate dihydrate, calcium pyrophosphate,tricalcium phosphate, calcium polymetaphosphate.

Colorants useful herein include as dyes, pigments and mixtures thereof.

Packaging Means

The cleaning implement herein may be combined in an article ofmanufacture with a packaging means.

The packaging means herein may be any suitable means known to packagecleaning implements. Indeed, particularly suitable packaging meansherein are selected from the group consisting of: paper bags, plasticbags, cartons, carton boxes, flow wraps, plastic wraps, and paper wraps,and the like and combinations thereof.

The packaging means herein may be printed and/or modified. Inparticular, such printing and/or other modification may be used toassociate a brand-name and/or logo of a hard surface cleaner with saidcleaning implement.

Method of Cleaning a Hard Surface

In another embodiment the present invention encompasses method ofcleaning a hard surface with a cleaning implement as described hereinabove.

In yet another embodiment herein, the present invention encompasses amethod of cleaning a hard surface by bringing a cleaning implementaccording to the present invention into contact with said hard surface.By “cleaning” it is meant herein removing spots and/or stains from hardsurfaces.

In still another embodiment herein, the present invention encompasses amethod of cleaning a hard surface with cleaning implement according tothe present invention.

Suitable hard surfaces herein are tiles, walls, floors, sanitaryfittings such as sinks, showers, shower curtains, wash basins, WCs,household appliances including, but not limited to, refrigerators,freezers, washing machines, automatic dryers, ovens, microwave ovens,dishwashers and so on.

The methods of cleaning a hard surface according to the presentinvention may additionally include the step of wetting said cleaningimplement or said foam with an appropriate solvent, preferably tapwater, more preferably water in combination with a detergentcomposition, prior to bringing said cleaning implement into contact withsaid hard surface.

EXAMPLES

Methods of Measurement:

Ram Pressure Value [N]:

All the ram pressure value measurements for assessing themechanical/resilient properties of the melamine-formaldehyde foams werecarried out as follows: A cylindrical steel ram 8 mm in diameter 10 cmin height was pressed at a right angle into a cylindrical foam sample 11cm in diameter and 5 cm in height until the foam sample broke. Themaximum force (unit: N) exerted by the ram until the foam sample brokeis hereinafter also referred to as ram pressure value and providesinformation about the mechanical/resilient quality of the foam. Thegreater the ram pressure values are, the better the mechanical/resilientproperties of the melamine-formaldehyde foams are; the further thevalues measured on any one melamine-formaldehyde foam parallel andperpendicularly to the direction of rise of the foam differ from eachother, the greater the anisotropy is and the worse the homogeneity is ofthe foam.

Compression set [%]:

All the compression set value measurements for assessing the elasticproperties of wet melamine formaldehyde foams were carried out asfollows:

A rectangular foam sample (cut into dimensions: 40 mm×40 mm, height: 25mm) is soaked in deionized water, and compressed for 60 min between twosteel plates (1 cm thickness) to either 20% (5 mm) or 8% (2 mm) of itsinitial height.

The compression set is determined by the following formula:C=(h0−hi)/h0, where h0 is the initial height before compression and hiis the sample thickness after compression. C0.5 denotes the compressionset after 30 min and C24 after 24 hours, respectively.

Compression Deflection Pressure Test Method:

The average Compression Deflection Pressure is determined using thestandard method ASTM D3575-14, (approved Jan. 1, 2014), according to theprocedures specified in Sections 1-8 and Suffix D (Sections 17-24) withthe following modifications: application of the method is extended toadditional polymer types including but not limited to melamineformaldehyde; the extent of compression (Sections 17, 22, and 23) is setat 70%; the sample is wetted prior to measurement by placing in a tub ofwater until eraser is fully submersed then immediately measured withoutcompressing prior to measurement; and the value of the compressiondeflection force per unit area of specimen in equation 2 of Section 22and in Section 23 is reported in units of psi. Both the averagethickness after pretest pressure and the average compression deflectionforce as specified in Section 23 are record.

Cumulative Pore Volume Test Method:

The Cumulative Pore Volume Test Method is used to determine theCumulative Pore Volume D₉₀/D₁₀ Ratio. This method makes use of stepped,controlled differential pressure and measurement of associated fluidmovement to characterize the distribution of effective pore radii thatexist in a material specimen within the range of 10 to 800 μm.

Method Principle

For uniform cylindrical pores, the radius of a pore is related to thedifferential pressure required to fill or empty the pore by the equationDifferential pressure=(2γ cos Θ)/r,where γ=liquid surface tension, Θ=contact angle, and r=pore radius.

Pores contained in natural and manufactured porous materials are oftenthought of in terms such as voids, holes or conduits, and these poresare generally not perfectly cylindrical nor all uniform. One cannonetheless use the above equation to relate differential pressure to aneffective pore radius, and by monitoring liquid movement into or out ofthe material as a function of differential pressure characterize theeffective pore radius distribution in a porous material. (Becausenonuniform pores are approximated as uniform by through the use of aneffective pore radius, this general methodology may not produce resultsprecisely in agreement with measurements of void dimensions obtained byother methods such as microscopy.)

The Cumulative Pore Volume Method uses the above principle and isreduced to practice using the apparatus and approach described in“Liquid Porosimetry: New Methodology and Applications” by B. Miller andI. Tyomkin published in The Journal of Colloid and Interface Science(1994), volume 162, pages 163-170, incorporated herein by reference.This method relies on measuring the increment of wetting(low-contact-angle) liquid volume that enters or leaves a porousmaterial as the differential air pressure is changed between ambient(“lab”) air pressure and a slightly elevated air pressure (positivedifferential pressure) surrounding the specimen in a sample testchamber. The specimen is introduced to the sample chamber dry, and thesample chamber is controlled at a positive differential pressure(relative to the lab) to prevent fluid uptake into the specimen afterthe fluid bridge is opened. After opening the fluid bridge, thedifferential air pressure is decreased in steps (but remains positive),subpopulations of pores acquire liquid according to their effective poreradius. After reaching a minimal (though positive) differential pressure(corresponding to the largest effective pore radius of interest in thespecimen) at which the specimen fluid within the fluid is at a maximum,differential pressure is increased stepwise again toward the startingpressure, and the liquid is drained from the specimen. It is during thislatter draining sequence (from lowest differential pressure, or largestcorresponding effective pore radius, to the largest differentialpressure, or smallest corresponding effective pore radius), thatcumulative volume distribution is determined in this method. Normalizingto the maximum volume of fluid acquired by the sample (at lowestdifferential pressure), the cumulative pore volume distribution (as afunction of differential pressure, and therefore effective pore radius)is determined by recursively subtracting the incremental volume ofliquid drained from the specimen upon each increase in differentialpressure step, and this incremental volume is associated with thesetpoint of differential pressure (and therefore its effective poreradius) for each particular step.

Sample Conditioning and Specimen Preparation

The Cumulative Pore Volume Method is conducted on samples that have beenconditioned in a conditioned room at a temperature of 23° C.±2.0° C. anda relative humidity of 45%±10% for a minimum of 12 hours prior to thetest. Except where noted all tests are conducted in such conditionedroom, all tests are conducted under the same environmental conditionsand in such conditioned room. Any damaged product or samples that havedefects such as wrinkles, tears, holes, and similar are not tested.Samples conditioned as described herein are considered dry samples forpurposes of this invention. Three specimens are measured for any givenmaterial being tested, and the results from those three replicates areaveraged to give the final reported value. Each of the three replicatespecimens has dimensions of 15 mm×55 mm×55 mm, and the broad surfacesare made parallel and microscopically flat. If no sample available islarge enough to create specimens of this size, a smaller specimen may beused with using an acrylic plate (below) sized to maintain the sameapplied pressure.

One of skill understands that involve several preparation steps, whichmay include the removal of all cleaning liquid and the separation of thevarious ply sheets from each other and from other components of thefinished article. Furthermore, one of skill understands it is importantto ensure the preparation does not damage the ply being tested or alterthe measured pore volume characteristics.

Apparatus

Apparatus suitable for this method is described in: “Liquid Porosimetry:New Methodology and Applications” by B. Miller and I. Tyomkin publishedin The Journal of Colloid and Interface Science (1994), volume 162,pages 163-170. Further, any pressure control scheme capable ofcontrolling the sample chamber pressure between 5 mm H₂O and 1000 mm H₂Odifferential pressure may be used in place of the pressure-controlsubsystem described in this reference. One example of suitable overallinstrumentation and software is the TRI/Autoporosimeter (TextileResearch Institute (TRI)/Princeton Inc. of Princeton, N.J., U.S.A.). TheTRI/Autoporosimeter is an automated computer-controlled instrument formeasuring pore volume distributions in porous materials (e.g., thevolumes of different size pores within the range from 1 to 1000 μmeffective pore radii). Computer programs such as Automated InstrumentSoftware Releases 2000.1 or 2003.1/2005.1; or Data Treatment SoftwareRelease 2000.1 (available from TRI Princeton Inc.), and spreadsheetprograms may be used to capture and analyse the measured data.

Method Procedure

The wetting liquid used is a 0.1% by weight solution of octylphenoxypolyethoxy ethanol (Triton X-100, a non-ionic surfactant available fromThe Dow Chemical Co., Midland, Mich.) in distilled water. Liquid densityis 1.00 g/cm³, surface tension γ to be 30 mN/m, and the contact angle Θto be 0° such that cos Θ=1. A 90-mm diameter mixed-cellulose-esterfilter membrane with a characteristic pore size of 0.22 μn (suchMillipore Corporation of Bedford, Mass., Catalog #GSWP09000) is affixedto the porous frit (monel or 316 stainless steel, media grade 80 fromMott Corp., Farmington, Conn., or equivalent) of the sample chamber.

A 4 cm×4 cm acrylic plate weighing 32 g is placed on the sample toensure the sample rests flat on the filter membrane during measurement.No additional weight is placed on the sample.

The sequence of differential pressures that are run in the test, in mmH₂O is as follows: 612.6, 306.3, 204.2, 153.2, 122.5, 102.1, 87.5, 76.6,68.1, 61.3, 51.0, 43.8, 38.3, 34, 30.6, 27.8, 25.5, 23.6, 21.9, 20.4,17.5, 15.3, 13.6, 12.3, 11.1, 10.2, 9.4, 8.8, 8.2, 7.7, 8.2, 8.8, 9.4,10.2, 11.1, 12.3, 13.6, 15.3, 17.5, 20.4, 21.9, 23.6, 25.5, 27.8, 30.6,34, 38.3, 43.8, 51.0, 61.3, 68.1, 76.6, 87.5, 102.1, 122.5, 153.2,204.2, 306.3, and 612.6. The criterion for moving from one pressure stepto the next is that fluid uptake/drainage from the specimen is measuredto be less than 15 μL/min.

Determination of Cumulative Pore Volume D₉₀/D₁₀ Ratio from CumulativePore Volume Distributions

The cumulative pore volume distributions (that is, normalized cumulativepore volume as a function of effective pore radius) for the threespecimens measured are averaged. D₉₀ is defined as the effective poreradius at which the cumulative pore volume distribution function has avalue of 0.90. If no measured data point satisfies this, D₉₀ isdetermined by a linear interpolation between the two data pointsimmediately proximal. Similarly, D₁₀ is defined as the effective poreradius at which the cumulative pore volume distribution function has avalue of 0.10. If no measured data point satisfies this, D₁₀ isdetermined by a linear interpolation between the two data pointsimmediately proximal. The quotient of D₉₀ and D₁₀ is the Cumulative PoreVolume D₉₀/D₁₀ Ratio.

Materials Used:

-   -   MF Melamine-formaldehyde precondensate having an average        molecular weight (number average) M of 350 g/mol, with a molar        ratio of melamine:formaldehyde of 1:3.    -   aS C12/C14-alkyl sulfate, sodium salt.    -   nS alkyl polyethylene glycol ether made from a linear, saturated        C16/C18 fatty alcohol.    -   E1000 Pluriol® E1000 (Polyethylene glycol with an number average        molecular weight of 1000)    -   E4000 Pluriol® E4000 (Polyethylene glycol with an number average        molecular weight of 4000)    -   E6000 Pluriol® E6000 (Polyethylene glycol with an number average        molecular weight of 6000)    -   E8000 Pluriol® E8000 (Polyethylene glycol with an number average        molecular weight of 8000)    -   eG ethoxylated glycerol with an average molecular weight of 310        g/mol    -   eTMP ethoxylated trimethylolpropane with an number average        molecular weight of 670 g/mol

Example 1

In a first step, 100 parts by weight of the melamine-formaldehydeprecondensate, MF, 38 parts of water, 1.2 parts of anionic surfactantaS, 0.3 parts of non-ionic surfactant nS, 2.5 parts of sodium formate,3.0 parts of formic acid, 0.5 parts of polyethylene glycol Pluriol®E4000 and 18 parts of the pentane were mixed with one another at atemperature of 20 to 35° C. The mixture was introduced into a foamingmold of polypropylene and irradiated in a microwave oven with microwave.The foam bodies obtained after microwave irradiation were annealed in acirculating air oven at 200° C. for 20 min.

Example 2

Example 1 was repeated with the difference that 1.0 parts Pluriol® E4000 were used.

Examples 3 to 5

Example 1 was repeated with the difference that 0.5 parts Pluriol® E6000, E8000 and E1000 were used.

Example 6

Example 1 was repeated with the difference that 20 parts pentane wereused.

Example 7

Example 1 was repeated with the difference that 0.5 parts ethoxylatedglycerol were used.

Example 8

Example 1 was repeated with the difference that 0.5 parts ethoxylatedtrimethylolpropane were used.

Comparative Examples C1 and C2

Example 1 was repeated with the difference that no polyethylenglycol wasadded and 18 parts (C1) and 16 parts (C2) pentane were added.

Density and mechanical data (ram pressure, compression sets C0.5 andC24, compression strength) of the foams are summarized in Table 1. Alldata are the average of 3 measurements.

Comparative Examples C3, C4 and C5

Aqueous solutions of Pluriol E4000 are prepared by dissolving the PEG indeionized water under magnetic stirring to yield a concentration of 1%wt.

Melamine-formaldehyd foam samples cut to dimensions of 122×67×30 mm³ aresoaked with the solution in an aluminum tray and pressed out by handthree times to remove excess water. Afterwards the samples are dried for6 h in an oven at 70° C. till they reach constant weight.

The weight of the samples after drying compared to the dry mass beforeimpregnation allows to calculate the loading of the foams with PEG.

The samples are rinsed by putting them in an aluminum tray filled with250 ml of deionized water at room temperature where they are allowed tosoak and are afterwards pressed out by hand three times. Afterwards thefoams are flipped over and the procedure is repeated.

The washing water was analyzed for its concentration of PEG.

TABLE 1 Type and amount of polymeric additive added per 100 parts ofmelamine- formaldehyde precondensate and physical and mechanicalproperties of the foams of Examples 1 to 7 and comparative Examples C1to C3 Example C1 C2 1 2 3 4 5 6 7 8 Type of additive — — E4000 E4000E6000 E8000 E1000 E4000 eG eTMP parts of additive — — 0.5 1 0.5 0.5 0.50.5 0.5 0.5 added Density, g/L 9 11 9 8 9 8 9 11 8 8 Ram pressure, N 3420 44 39 39 34 36 32 49 41 Compression set 75 82 58 73 70 73 73 68 78 80C0.5, % Compression set 35 41 17 32 31 33 35 30 40 40 C24, %

TABLE 2 Concentration of PEG found in the washing water after soaking inwater Example 1 C3 Sample Foamed with 0.5 parts Impregnated with 1%aqueous Pluriol ® 4000 solution of Pluriol ® 4000 mg/ml Pluriol ® 0 0.5

A piece of melamine-formaldehyde foam comprising linear polymeraccording to present invention is used to clean a hard surface bywetting a piece of said foam with water and thereafter bringing it intocontact with the hard surface to be cleaned. The foam according thepresent invention shows an excellent performance in removing greasy soapscum and neat kitchen dirt from said hard surface, whilst providingsurface safety.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A cleaning implement comprisingmelamine-formaldehyde foam, wherein the melamine-formaldehyde foamcomprises 0.5 weight % of at least one linear polymer with a numberaverage molecular weight M_(n) in the range of 4000 g/mol, wherein thelinear polymer is polyethylene glycol, wherein the cleaning implement isobtained by foaming and crosslinking a mixture of amelamine-formaldehyde precondensate and the linear polymer.
 2. Thecleaning implement according to claim 1, wherein themelamine-formaldehyde foam has a density in the range from about 8 toabout 12 kg/m³.
 3. The cleaning implement according to claim 1, whereinthe melamine-formaldehyde foam has a compression set after 24 hoursbelow about 25%.
 4. The cleaning implement according to claim 1, whereinthe melamine-formaldehyde foam has a Ram Pressure above about 35 N. 5.The cleaning implement according to claim 1, wherein themelamine-formaldehyde foam is formed by the process of heating andfoaming an aqueous mixture M using microwave radiation, said mixture Mcomprising at least one melamine-formaldehyde precondensate, at leastone curative, at least one surfactant, at least one blowing agent andthe at least one linear polymer.
 6. The cleaning implement according toclaim 5, wherein said mixture M comprises a surfactant mixturecomprising a mixture of 50 to 90 wt % of an anionic surfactant and 10 to50 wt % of nonionic surfactants, wherein the weight percentages are eachbased on the total weight of the surfactant mixture.
 7. The cleaningimplement according to claim 5, wherein the curative is formic acid. 8.The cleaning implement according to claim 5, wherein the blowing agentis pentane.
 9. A process of producing the cleaning implement accordingto claim 5, comprising the steps of: a) producing an aqueous mixture Mcomprising 100 parts by weight of the melamine-formaldehydeprecondensate, 2 to 4 parts by weight of the curative, 0.2 to 5 parts byweight of a surfactant mixture, 0.1 to 5 parts by weight of at least onesalt of an inorganic acid and/or of an organic carboxylic acid, 1 to 40parts by weight of the blowing agent, 0.1 to 5 parts by weight of the atleast one linear, polymer, 0 to 20 parts by weight of one or morefurther additives, and 25 to 60 parts by weight of water, b) heating andfoaming said mixture M using microwave radiation, c) annealing the foamusing hot air and/or nitrogen in a temperature range from 150° C. to290° C.
 10. The cleaning implement according to claim 1, wherein themelamine-formaldehyde foam comprises a benefit agent selected from thegroup consisting of a detergent composition; surfactants; dyes; inks;pigments; scents; acids; bases; oils; salts; bleach; antimicrobialagents; fragrances; solvents; biocides; hydrophobicizing agents; agentsinfluencing haptics; agents influencing the soil release behavior;formaldehyde scavengers; abrasives such as inorganic.
 11. The cleaningimplement according to claim 1, further comprising a second layer.
 12. Amethod of cleaning a hard surface comprising bringing the cleaningimplement according to claim 1 into contact with a hard surface.